本發明係關於一種III族元素氮化物基板之檢查方法、III族元素氮化物基板之製造方法及半導體元件之製造方法。The present invention relates to a method for inspecting a Group III nitride substrate, a method for manufacturing a Group III nitride substrate, and a method for manufacturing a semiconductor device.
III族元素氮化物具有直接躍遷型之寬能隙，且具有高絕緣破壞電場(dielectric breakdown field)、高電子飽和速度，故而作為例如射頻/高功率之電子器件用之半導體材料而熱烈地受到開發。Group III nitrides have wide band gaps with direct-transition properties, high dielectric breakdown fields, and high electron saturation velocities. Therefore, they are being actively developed as semiconductor materials for applications such as radio-frequency and high-power electronic devices.
例如專利文獻1所記載般，根據用途，上述III族元素氮化物希望為高電阻。For example, as described in Patent Document 1, the Group III element nitride is desired to have high resistance depending on the application.
〔先前技術文獻〕[Prior Art Literature]
〔專利文獻〕[Patent Literature]
[專利文獻1]日本第5451085號公報[Patent Document 1] Japan Gazette No. 5451085
由上述高電阻之III族元素氮化物基板所得之半導體元件存在有品質之均勻性不夠充分的情況，而希望提升良率。Semiconductor devices made from the aforementioned high-resistance Group III nitride substrates suffer from insufficient quality uniformity, and there is a desire to improve the yield.
有鑒於上述課題，本發明之主要目的在於提供一種可提升良率之III族元素氮化物基板。In view of the above issues, the main purpose of this invention is to provide a Group III nitride substrate that can improve yield.
1.本發明之實施形態之III族元素氮化物基板之檢查方法包含下列步驟：準備摻雜有III族元素以外之元素之III族元素氮化物基板；將激發能量照射至該III族元素氮化物基板；以及測定藉由該照射所獲得之發射光譜之能帶邊緣發光之半值寬。1. The inspection method for a Group III nitride substrate according to an embodiment of the present invention comprises the following steps: preparing a Group III nitride substrate doped with an element other than a Group III element; irradiating the Group III nitride substrate with excitation energy; and measuring the half-value width of the band edge luminescence in the emission spectrum obtained by the irradiation.
2.上述1之檢查方法中，上述激發能量之照射亦可藉由照射紫外光或電子束之至少一者來進行。2. In the inspection method described in 1 above, the excitation energy may be irradiated by at least one of ultraviolet light or electron beam.
3.上述1或2之檢查方法中，亦可針對上述III族元素氮化物基板之主面，而將上述激發能量照射至複數部位。3. In the inspection method 1 or 2 above, the excitation energy may be irradiated to multiple locations on the primary surface of the Group III nitride substrate.
4.上述1至3中任一者之檢查方法中，上述III族元素以外之元素亦可包含過渡元素。4. In any of the inspection methods 1 to 3 above, elements other than the Group III elements may also include transition elements.
5.上述4之檢查方法中，上述過渡元素亦可包含鐵或錳之至少一種。5. In the inspection method of 4 above, the transition element may also include at least one of iron or manganese.
6.上述1至5中任一者之檢查方法中，上述III族元素氮化物基板亦可包含氮化鎵。6. In any of the inspection methods 1 to 5 above, the Group III nitride substrate may also include gallium nitride.
7.上述1至6中任一者之檢查方法中，上述III族元素氮化物基板中，藉由電荷量時間變化所求得之電阻率亦可為1×105Ω‧cm以上。7. In the inspection method according to any one of 1 to 6 above, the resistivity of the group III nitride substrate obtained by the time variation of the charge amount may be 1×105 Ω·cm or more.
8.上述1至7中任一者之檢查方法中，上述半值寬為半高全寬。8. In any of the inspection methods 1 to 7 above, the half-value width is the full width at half height.
9.上述1至7中任一者之檢查方法中，上述半值寬為半高半寬。9. In any of the inspection methods 1 to 7 above, the half-value width is half-height half-width.
10.本發明之另一實施形態之III族元素氮化物基板之製造方法包含下列步驟：進行上述1至7中任一者之III族元素氮化物基板之檢查方法；以及基於上述能帶邊緣發光之半值寬，來挑選上述III族元素氮化物基板。10. Another embodiment of the present invention includes a method for manufacturing a Group III nitride substrate comprising the following steps: performing the Group III nitride substrate inspection method described in any one of 1 to 7 above; and selecting the Group III nitride substrate based on the half-value width of the band edge luminescence.
11.上述10之製造方法中，亦可挑選上述能帶邊緣發光之半高全寬為6.5nm以下之上述III族元素氮化物基板。11. In the manufacturing method of 10 above, the Group III nitride substrate may be selected such that the full width at half maximum of the band edge emission is 6.5 nm or less.
12.上述10之製造方法中，亦可挑選上述能帶邊緣發光之長波長側之半高半寬為4.2nm以下之上述III族元素氮化物基板。12. In the manufacturing method of 10 above, the Group III nitride substrate may be selected such that the half-width at half-maximum of the long-wavelength side of the band-edge emission is 4.2 nm or less.
13.上述10至12中任一者之製造方法中，準備上述III族元素氮化物基板之步驟亦可包含下列步驟：準備晶種基板，該晶種基板係具有具彼此呈對向之上表面及下表面之藍寶石基板以及形成在該藍寶石基板之上表面之晶種膜；以及於該晶種基板之該晶種膜上生長摻雜有III族元素以外之元素之III族元素氮化物結晶；該藍寶石基板之偏離角亦可為0.58°以下。13. In the manufacturing method of any one of 10 to 12 above, the step of preparing the Group III nitride substrate may also include the following steps: preparing a seed crystal substrate comprising a sapphire substrate having upper and lower surfaces facing each other and a seed film formed on the upper surface of the sapphire substrate; and growing a Group III nitride crystal doped with an element other than the Group III element on the seed film of the seed crystal substrate. The off angle of the sapphire substrate may also be 0.58° or less.
14.上述13之製造方法中，上述藍寶石基板之偏離角亦可為0.20°以上且0.42°以下。14. In the manufacturing method of 13 above, the offset angle of the sapphire substrate may be greater than 0.20° and less than 0.42°.
15.本發明之又一實施形態之半導體元件之製造方法包含下列步驟：將激發能量照射至摻雜有III族元素以外之元素之III族元素氮化物基板，並測定藉由該照射所獲得之發射光譜之能帶邊緣發光之半值寬；於該III族元素氮化物基板形成通道層及障壁層而獲得疊層構造；以及於該疊層構造上設置源極電極、汲極電極及閘極電極。15. A method for manufacturing a semiconductor device according to another embodiment of the present invention comprises the following steps: irradiating a Group III nitride substrate doped with an element other than a Group III element with excitation energy, and measuring the half-value width of the band-edge emission of the emission spectrum obtained by the irradiation; forming a channel layer and a barrier layer on the Group III nitride substrate to obtain a stacked structure; and providing a source electrode, a drain electrode, and a gate electrode on the stacked structure.
16.上述15之製造方法中，亦可將較上述通道層之構成材料之能隙能量要高之能量照射至上述III族元素氮化物基板。16. In the manufacturing method of 15 above, the Group III nitride substrate may be irradiated with energy higher than the energy gap energy of the material constituting the channel layer.
17.上述15或16之製造方法中，亦可獲得具備上述半值寬滿足既定值之上述III族元素氮化物基板之半導體元件。17. In the manufacturing method of 15 or 16 above, a semiconductor device having the above-mentioned Group III nitride substrate having the above-mentioned half-value width meeting a predetermined value can also be obtained.
18.上述15至17中任一者之製造方法中，亦可藉由磊晶成長來獲得上述疊層構造。18. In any of the manufacturing methods 15 to 17 above, the stacked structure can also be obtained by epitaxial growth.
19.本發明之又一實施形態之III族元素氮化物基板係摻雜有III族元素以外之元素，藉由激發能量之照射所獲得之發射光譜之能帶邊緣發光之半值寬為6.5nm以下。19. In another embodiment of the present invention, the Group III nitride substrate is doped with elements other than Group III elements, and the half-value width of the band edge luminescence of the emission spectrum obtained by irradiation with excitation energy is less than 6.5 nm.
20.本發明之又一實施形態之III族元素氮化物基板係摻雜有III族元素以外之元素，藉由激發能量之照射所獲得之發射光譜之能帶邊緣發光之長波長側之半高半寬為4.2nm以下。20. In another embodiment of the present invention, the Group III nitride substrate is doped with elements other than Group III elements, and the half-width at half-maximum of the long-wavelength side of the band edge emission spectrum obtained by irradiation with excitation energy is less than 4.2 nm.
21.上述19或20之III族元素氮化物基板中，上述III族元素氮化物基板亦可包含氮化鎵。21. In the Group III nitride substrate of 19 or 20 above, the Group III nitride substrate may also contain gallium nitride.
22.上述19到21中任一者之III族元素氮化物基板中，上述III族元素以外之元素亦可包含過渡元素。22. In the Group III nitride substrate according to any one of 19 to 21 above, the elements other than the Group III elements may also include transition elements.
23.上述22之III族元素氮化物基板中，上述過渡元素亦可包含鐵或錳之至少一種。23. In the Group III nitride substrate described in 22 above, the transition element may also include at least one of iron or manganese.
24.本發明之又一實施形態之III族元素氮化物基板之製造方法係上述19至23中任一者之III族元素氮化物基板之製造方法，亦可包含下列步驟：準備晶種基板，該晶種基板係具有具彼此呈對向之上表面及下表面之藍寶石基板以及形成在該藍寶石基板之上表面之晶種膜；以及於該晶種基板之該晶種膜上，生長摻雜有III族元素以外之元素之III族元素氮化物結晶；該藍寶石基板之偏離角亦可為0.58°以下。24. A method for manufacturing a Group III nitride substrate according to another embodiment of the present invention is the method for manufacturing a Group III nitride substrate according to any one of 19 to 23 above, further comprising the steps of: preparing a seed crystal substrate comprising a sapphire substrate having upper and lower surfaces facing each other and a seed film formed on the upper surface of the sapphire substrate; and growing a Group III nitride crystal doped with an element other than a Group III element on the seed film of the seed crystal substrate. The off angle of the sapphire substrate may also be 0.58° or less.
25.上述24之製造方法中，亦可藉由助熔劑法，來生長上述III族元素氮化物結晶。25. In the manufacturing method of 24 above, the Group III element nitride crystals may also be grown using a flux method.
根據本發明之實施形態，便可提供一種可提升良率之III族元素氮化物基板。According to the embodiments of the present invention, a Group III nitride substrate with improved yield can be provided.
10:III族元素氮化物基板10: Group III nitride substrate
11:第一主面11: First main surface
12:第二主面12: Second main surface
13:側面13:Side
16:III族元素氮化物結晶層16: Group III nitride crystal layer
20:晶種基板20: Seed substrate
21:基底基板21: Base substrate
21a:上表面21a: Upper surface
21b:下表面21b: Lower surface
22:晶種膜22: Seed film
30:疊層基板30: Laminated substrate
32:獨立基板32: Independent substrate
40:HEMT元件40: HEMT device
41:通道層41: Channel Layer
42:障壁層42: Barrier layer
43:疊層構造43: Layered structure
44:源極電極44: Source electrode
45:汲極電極45: Drain electrode
46:閘極電極46: Gate electrode
51:雷射裝置51: Laser device
52:截波器52:Chopper
53:消光板53: Matte board
54:聚光透鏡54: Focusing lens
55:試料台55: Sample table
56:測定基板56:Measurement substrate
57:聚光透鏡57: Focusing lens
58:聚光透鏡58: Focusing lens
59:分光器59: Spectrum Splitter
60:光檢出器60: Photodetector
61:鎖相放大器61: Phase-locked amplifier
[圖1]為表示本發明一實施形態相關之III族元素氮化物基板之概略構成之概略性的剖面圖。[Figure 1] is a schematic cross-sectional view showing the general structure of a Group III nitride substrate according to one embodiment of the present invention.
[圖2]為圖1所示之III族元素氮化物基板之平面圖。[Figure 2] is a plan view of the Group III nitride substrate shown in Figure 1.
[圖3A]為表示一實施形態相關之III族元素氮化物基板之製造步驟之圖。[Figure 3A] is a diagram showing the manufacturing steps of a Group III nitride substrate according to one embodiment.
[圖3B]為接續於圖3A之圖。[Figure 3B] is a continuation of Figure 3A.
[圖3C]為接續於圖3B之圖。[Figure 3C] is a continuation of Figure 3B.
[圖4]為表示本發明一實施形態相關之半導體元件之概略構成之概略性的剖面圖。[Figure 4] is a schematic cross-sectional view showing the schematic structure of a semiconductor device related to one embodiment of the present invention.
[圖5]為用以說明基板之發射光譜之測定方法之圖。Figure 5 illustrates the method for measuring the emission spectrum of a substrate.
[圖6]為實驗例1之氮化鎵基板之能帶邊緣附近之發射光譜。[Figure 6] shows the emission spectrum near the band edge of the gallium nitride substrate in Experimental Example 1.
[圖7]為實驗例1之氮化鎵基板之能帶邊緣附近之發射光譜。Figure 7 shows the emission spectrum near the band edge of the gallium nitride substrate in Experimental Example 1.
以下，便參照圖式就本發明之實施形態來說明，但本發明並不限定於該等實施形態。又，圖式係為了使說明更加明確，而有相較於實施形態，就各部之寬度、厚度、形狀等概略性地表示之情況，但僅為一例，而非限定解釋本發明。The following describes embodiments of the present invention with reference to the drawings, but the present invention is not limited to these embodiments. Furthermore, for the sake of clarity, the drawings may schematically illustrate the width, thickness, and shape of various components relative to the embodiments. However, these are merely examples and are not intended to limit the present invention.
A.III族元素氮化物基板A. Group III nitride substrate
圖1為表示本發明一實施形態相關之III族元素氮化物基板之概略構成之概略性的剖面圖，圖2為圖1所示之III族元素氮化物基板之平面圖。III族元素氮化物基板10為板狀，且具有彼此呈對向之第一主面11及第二主面12，該等係透過側面13來連接。Figure 1 is a schematic cross-sectional view illustrating the general structure of a Group III nitride substrate according to one embodiment of the present invention. Figure 2 is a plan view of the Group III nitride substrate shown in Figure 1 . The Group III nitride substrate 10 is plate-shaped and has a first principal surface 11 and a second principal surface 12 facing each other, which are connected via a side surface 13.
圖式範例中，III族元素氮化物基板雖成為圓盤狀(晶圓)，但不限於此，亦可為任意適當之形狀。III族元素氮化物基板之尺寸可對應於目的來適當設定。圓盤狀之III族元素氮化物基板之直徑係例如50mm以上且200mm以下。III族元素氮化物基板之厚度係例如250μm以上且800μm以下。In the example shown, the Group III nitride substrate is in a disk shape (wafer), but this is not limiting and may be any appropriate shape. The dimensions of the Group III nitride substrate can be appropriately set according to the intended purpose. The diameter of the disk-shaped Group III nitride substrate is, for example, greater than 50 mm and less than 200 mm. The thickness of the Group III nitride substrate is, for example, greater than 250 μm and less than 800 μm.
一實施形態中，III族元素氮化物基板之電阻率係例如1×105Ω‧cm以上且1×1012Ω‧cm以下，較佳為1×106Ω‧cm以上，更佳為1×107Ω‧cm以上。如此般之半絕緣性之III族元素氮化物基板可適合用為例如高電子移動速度電晶體(HEMT)元件之基板。具體而言，係於III族元素氮化物基板形成通道層及障壁層，並可將其作為HEMT元件來使用。In one embodiment, the resistivity of the Group III nitride substrate is, for example, greater than 1×105 Ω·cm and less than 1×1012 Ω·cm, preferably greater than 1×106 Ω·cm, and even more preferably greater than 1×107 Ω·cm. Such a semi-insulating Group III nitride substrate is suitable for use as a substrate for high electron mobility transistor (HEMT) devices, for example. Specifically, a channel layer and a barrier layer are formed on the Group III nitride substrate, and the resulting device can be used as a HEMT device.
上述III族元素氮化物基板之電阻率可藉由電荷量時間變化來求得。根據電荷量時間變化，便可不破壞III族元素氮化物基板而求得電阻率。具體而言，係將III族元素氮化物基板插入至由探針與台座所構成之電容器內，並施加脈衝電壓，來測定III族元素氮化物基板之電荷量之時間變化，再由測定值來算出電阻率。此時，由於探針並不接觸於III族元素氮化物基板，故而可不形成歐姆性接觸電極而求得電阻率。此外，探針之空間解析度可為1mm~10mm左右。關於電阻率之求得方法，係記載於例如非專利文獻之「R.Stibal et al.,“Contactless evaluation of semi-insulating GaAs wafer resistivity using the time-dependent charge measurement”Semiconductor Science and Technology 6 p995(1991)」。The resistivity of the Group III nitride substrate can be determined by analyzing the time variation of the charge. This allows the resistivity to be determined without damaging the Group III nitride substrate. Specifically, the Group III nitride substrate is inserted into a capacitor formed by a probe and a pedestal. A pulse voltage is applied to measure the time variation of the charge on the Group III nitride substrate, and the resistivity is calculated from the measured value. Since the probe does not contact the Group III nitride substrate, the resistivity can be determined without forming an ohmic contact. Furthermore, the spatial resolution of the probe can be approximately 1mm to 10mm. The method for determining resistivity is described in, for example, the non-patent document "R. Stibal et al., "Contactless evaluation of semi-insulating GaAs wafer resistivity using the time-dependent charge measurement" Semiconductor Science and Technology 6 p995 (1991).
III族元素氮化物基板係由III族元素氮化物結晶所構成。作為構成III族元素氮化物之III族元素可使用例如鋁(Al)、鎵(Ga)、銦(In)。該等可單獨、或是組合二種以上來使用。作為III族元素氮化物之具體例，可列舉：氮化鋁(AlxN)、氮化鎵(GayN)、氮化銦(InzN)、氮化鋁鎵(AlxGayN)、氮化鎵銦(GayInzN)、氮化鋁銦(AlxInzN)、氮化鋁鎵銦(AlxGayInzN)。此外，括弧內之各化學式中，就代表性而言係x+y+z=1。The Group III nitride substrate is composed of Group III nitride crystals. Group III elements constituting Group III nitrides include aluminum (Al), gallium (Ga), and indium (In). These elements can be used alone or in combination of two or more. Specific examples of Group III nitrides include aluminum nitride (AlxN ), gallium nitride (GayN ), indium nitride (InzN ), aluminum gallium nitride (AlxGayN ),gallium indium nitride (GayInzN ), aluminumindium nitride (AlxInzN ), and aluminum galliumindium nitride (AlxGayInzN ). In the chemical formulas in parentheses, x+y +z =1 is representative.
上述III族元素氮化物係摻雜有III族元素以外之元素。具體而言，III族元素氮化物係包含III族元素以外之元素來作為摻雜劑。藉由摻雜有III族元素以外之元素，可獲得能良好地滿足上述電阻率之III族元素氮化物基板(半絕緣性之III族元素氮化物基板)。作為上述摻雜劑，較佳為鐵(Fe)、錳(Mn)、釩(V)、鉻(Cr)、鈷(Co)、鎳(Ni)等過渡元素。該等可單獨、或是組合二種以上來使用。較佳為，過渡元素包含鐵或錳之至少一種。III族元素氮化物基板中之過渡元素之存在量係例如5×1016atoms/cm3以上且1×1020atoms/cm3以下。The above-mentioned Group III nitride is doped with elements other than Group III elements. Specifically, the Group III nitride contains elements other than Group III elements as dopants. By doping with elements other than Group III elements, a Group III nitride substrate (a semi-insulating Group III nitride substrate) that satisfies the above-mentioned resistivity can be obtained. Preferred dopants include transition elements such as iron (Fe), manganese (Mn), vanadium (V), chromium (Cr), cobalt (Co), and nickel (Ni). These can be used alone or in combination of two or more. Preferably, the transition element includes at least one of iron or manganese. The amount of the transition element in the Group III nitride substrate is, for example, not less than 5×1016 atoms/cm3 and not more than 1×1020 atoms/cm3 .
上述III族元素氮化物結晶中，代表性而言，<0001>方向為c軸方向，<1-100>方向為m軸方向，<11-20>方向為a軸方向。又，正交於c軸之結晶面為c面，正交於m軸之結晶面為m面，正交於a軸之結晶面為a面。一實施形態中，III族元素氮化物基板10之厚度方向係平行或略平行於c軸，第一主面11係(0001)面側之III族元素極性面，第二主面12係(000-1)側之氮極性面。第一主面11亦可平行於(0001)面，亦可相對於(0001)面而傾斜。第一主面11相對於(0001)面之傾斜角係例如10°以下，亦可為5°以下，亦可為2°以下，亦可為1°以下。第二主面12亦可平行於(000-1)面，亦可相對於(000-1)面而傾斜。第二主面12相對於(000-1)面之傾斜角係例如10°以下，亦可為5°以下，亦可為2°以下，亦可為1°以下。In the aforementioned Group III nitride crystal, the <0001> direction is typically the c-axis, the <1-100> direction is the m-axis, and the <11-20> direction is the a-axis. Furthermore, the crystal plane perpendicular to the c-axis is the c-plane, the crystal plane perpendicular to the m-axis is the m-plane, and the crystal plane perpendicular to the a-axis is the a-plane. In one embodiment, the thickness direction of the Group III nitride substrate 10 is parallel or approximately parallel to the c-axis, the first principal surface 11 is a Group III polar surface on the (0001) side, and the second principal surface 12 is a nitrogen polar surface on the (000-1) side. The first principal surface 11 may be parallel to the (0001) plane or tilted relative to the (0001) plane. The tilt angle of the first principal surface 11 relative to the (0001) plane may be, for example, 10° or less, 5° or less, 2° or less, or 1° or less. The second principal surface 12 may be parallel to the (000-1) plane or tilted relative to the (000-1) plane. The tilt angle of the second principal surface 12 relative to the (000-1) plane may be, for example, 10° or less, 5° or less, 2° or less, or 1° or less.
B.檢查方法B. Inspection Methods
上述III族元素氮化物基板即便在藉由上述電荷量時間變化所求得之電阻率滿足既定值(例如1×105Ω‧cm以上)的情況，仍被認為存在有在III族元素氮化物基板之面內，存在電阻率低之區域的情況。具體而言，係因III族元素氮化物結晶內之錯位等的結晶缺陷，使氧等的雜質元素偏析，而有可能對導電性造成影響。因結晶缺陷容易使氧等的施體性雜質混入，而有可能對電阻率造成影響。因此，在III族元素氮化物基板面內，被認為有結晶缺陷集中在例如φ10μm~200μm左右之微小區域的情況。另一方面，利用上述電荷量時間變化所進行之電阻率之測定方法之測定探針的直徑可為例如φ1mm~10mm。在利用電荷量時間變化所進行之電阻率之測定中，係以至少在此測定探針之直徑的範圍中電阻率為均勻為前提，而被認為難以正確地測定局部性地包含電阻率低之微小區域之區域的電阻率。又，對應於電阻率低之區域而獲得之半導體元件有品質降低之虞。例如，對應於電阻率低之區域而獲得之HEMT元件有產生漏電流之虞。Even when the resistivity of the Group III nitride substrate, as determined by the time-dependent charge variation, satisfies a predetermined value (e.g., 1×105 Ω·cm or greater), it is thought that regions of low resistivity exist within the surface of the Group III nitride substrate. Specifically, crystal defects such as dislocations within the Group III nitride crystals cause the segregation of impurity elements such as oxygen, potentially affecting conductivity. Crystal defects facilitate the incorporation of donor impurities such as oxygen, potentially affecting resistivity. Consequently, it is thought that within the surface of the Group III nitride substrate, crystal defects are concentrated in tiny regions, for example, approximately 10μm to 200μm in diameter. On the other hand, the diameter of the measuring probe used in the resistivity measurement method using the time-dependent charge flow can be, for example, 1 mm to 10 mm. Resistivity measurement using the time-dependent charge flow assumes uniform resistivity at least within the probe's diameter. However, accurately measuring the resistivity of areas containing localized, microscopic regions of low resistivity is considered difficult. Furthermore, semiconductor devices obtained from these low-resistivity regions may suffer from reduced quality. For example, HEMT devices obtained from these low-resistivity regions may generate leakage current.
本發明一實施形態相關之III族元素氮化物基板之檢查方法包含：將激發能量照射至準備好之上述III族元素氮化物基板；以及測定藉由照射所獲得之發射光譜之能帶邊緣發光之半值寬。One embodiment of the present invention relates to a method for inspecting a Group III nitride substrate, comprising: irradiating a prepared Group III nitride substrate with excitation energy; and measuring the half-value width of the band-edge luminescence in the emission spectrum obtained by the irradiation.
上述激發能量之照射可例如藉由照射紫外光或電子束之至少一者來進行。一實施形態中，係於上述III族元素氮化物基板照射較上述通道層之構成材料之能隙能量要高之能量。藉由照射如此般之能量，便可良好地預測例如HEMT元件之漏電流之產生。The excitation energy can be applied, for example, by irradiating at least one of ultraviolet light and an electron beam. In one embodiment, the Group III nitride substrate is irradiated with an energy higher than the bandgap energy of the material forming the channel layer. By irradiating with such an energy, leakage current generation in, for example, a HEMT device can be accurately predicted.
上述紫外光之照射可使用例如能發射出短於能帶邊緣之波長的雷射光之光源。作為雷射光源，代表性而言，可使用He-Cd雷射或準分子雷射。又，紫外光之照射亦可使用例如低壓水銀燈、氘燈等的深紫外光(DUV)燈。For the ultraviolet light irradiation, a light source capable of emitting laser light with a wavelength shorter than the band edge can be used. Representative laser light sources include He-Cd lasers and excimer lasers. Furthermore, deep ultraviolet (DUV) lamps such as low-pressure mercury lamps and deuterium lamps can also be used for ultraviolet light irradiation.
上述電子束之照射可使用例如能量為0.5KeV~10KeV左右之電子束源(例如電子槍)。作為電子束源，可列舉例如：冷陰極場放射電子源、光陰極電子源、蕭特基(Schottky)電子源。The electron beam irradiation can be performed using an electron beam source (e.g., an electron gun) with an energy of approximately 0.5 KeV to 10 KeV. Examples of electron beam sources include cold cathode field emission electron sources, photocathode electron sources, and Schottky electron sources.
例如，亦可於以氮化鎵所構成之III族元素氮化物基板照射波長364nm以下之紫外光。由具有較氮化鎵要高之能隙能量之氮化鋁鎵所構成之III族元素氮化物基板係可能需要更高之能量，故而亦可照射電子束。For example, a III-nitride substrate composed of gallium nitride can be irradiated with ultraviolet light of a wavelength below 364nm. A III-nitride substrate composed of aluminum gallium nitride, which has a higher bandgap energy than gallium nitride, may require even higher energy and can therefore also be irradiated with an electron beam.
藉由激發能量朝上述III族元素氮化物基板之照射所獲得之發射光譜之測定，代表性而言，可使用任意適當之紫外線檢出器來進行使用分光器分光後之任意波長之光的強度之測定。作為紫外線檢出器，可例示有Si光二極體、光電子倍增管(PMT)等。又，作為紫外線檢出器，可例示有將小型光柵與CCD/CMOS/NMOS影像感應器組合之陣列型分光檢出器等。The emission spectrum obtained by irradiating the Group III nitride substrate with excitation energy can typically be measured using any appropriate UV detector to measure the intensity of light of any wavelength after separation using a spectrometer. Examples of UV detectors include Si photodiodes and photomultiplier tubes (PMTs). Another example of a UV detector is an array-type spectroscopic detector that combines a small grating with a CCD/CMOS/NMOS image sensor.
從測定之發射光譜來獲得能帶邊緣發光之半值寬。藉由使測定之半值寬滿足既定值(藉由具有既定值以下)，便可獲得品質優異之半導體元件。例如，可獲得經抑制漏電流之HEMT元件。然後，藉由挑選使用可滿足既定之半值寬之III族元素氮化物基板，便可大幅度地提升半導體元件製造之良率。此處，半值寬包含半高全寬(FWHM)及半高半寬(HWHM)。一實施形態中，測定之發射光譜之能帶邊緣發光之半高全寬較佳為6.5nm以下。另一實施形態中，測定之發射光譜之能帶邊緣發光之長波長側之半高半寬較佳為4.2nm以下。The half-width of the band-edge luminescence is obtained from the measured emission spectrum. By ensuring that the measured half-width satisfies a predetermined value (or is below the predetermined value), a high-quality semiconductor device can be obtained. For example, a HEMT device with suppressed leakage current can be obtained. Then, by selecting and using a III-nitride substrate that meets the predetermined half-width, the yield of semiconductor device manufacturing can be significantly improved. Here, the half-width includes the full width at half height (FWHM) and the half-width at half height (HWHM). In one embodiment, the half-width of the band-edge luminescence of the measured emission spectrum is preferably below 6.5 nm. In another embodiment, the half-width at half-maximum of the long-wavelength side of the band-edge emission of the measured emission spectrum is preferably less than 4.2 nm.
將激發能量照射至上述半絕緣性之III族元素氮化物基板所得之發射光譜之強度相較於將激發能量照射至導電性之III族元素氮化物基板(例如未摻雜有III族元素以外之元素之III族元素氮化物基板)所得之發射光譜之強度，可為微弱，且容易因基板之表面平坦性或加工變質層(altered layer)之有無而受到影響。然而，本發明人在細查半絕緣性之III族元素氮化物基板之發射光譜與所得之半導體元件之品質的關係時，發現到在能帶邊緣發光之半值寬與所得之半導體元件之品質存在有關連性。具有良好之半絕緣性之III族元素氮化物中，雖發射光譜之能帶邊緣強度可成為微弱，但由於透過能帶邊緣附近之各種位階的發光係相對性地下降，故而在外觀上，半值寬可變窄。另一方面，例如若將氧等的施體性雜質導入至III族元素氮化物結晶內，則使能帶邊緣附近之發光強度變強，且可使半值寬變寬。The intensity of the emission spectrum obtained by irradiating the semi-insulating Group III nitride substrate with excitation energy can be weak compared to the intensity of the emission spectrum obtained by irradiating a conductive Group III nitride substrate (e.g., a Group III nitride substrate not doped with elements other than Group III elements). This intensity is also easily affected by the substrate's surface flatness or the presence of an altered layer. However, the inventors, while carefully examining the relationship between the emission spectrum of the semi-insulating Group III nitride substrate and the quality of the resulting semiconductor device, discovered a correlation between the half-value width of the band edge emission and the quality of the resulting semiconductor device. In Group III nitrides, which exhibit excellent semi-insulating properties, the band edge intensity of the emission spectrum can be weak. However, since the emission through various levels near the band edge is relatively reduced, the half-value width can be narrowed. On the other hand, introducing donor impurities such as oxygen into the Group III nitride crystal can enhance the emission intensity near the band edge and broaden the half-value width.
藉由能帶邊緣發光之半值寬，便可簡易地判斷在室溫下之測定中之III族元素氮化物基板的好壞。嚴格來說，發射光譜相對於在能帶邊緣附近中可能包含各種能階之發光，且僅能在極低溫下分離而被觀測之情況，能帶邊緣發光之半值寬可在室溫下測定。又，能帶邊緣發光之半值寬之測定有測定裝置之裝置依存性低之傾向。具體而言，無需將照射之激發能量之強度調整為固定，或是確認較正用試料之再現性。The half-width (HWHM) of band-edge emission (BLE) allows for easy evaluation of the quality of Group III nitride substrates during room-temperature measurements. Specifically, whereas the emission spectrum near the band edge may contain emission at various energy levels and can only be isolated and observed at extremely low temperatures, the HWHM of BLE can be measured at room temperature. Furthermore, measuring the HWHM of BLE tends to be less dependent on the measurement setup. Specifically, there is no need to maintain a constant level of excitation energy or verify reproducibility with a properly used sample.
激發能量之照射亦可照射至上述III族元素氮化物基板之主面之複數部位。藉由照射至複數部位，並映射基板面內之能帶邊緣發光之半值寬，便可預測未滿足既定值之區域會成為所得之半導體元件之品質低之區域(例如漏電流大之不良區域)。例如，在圖2所示之圓盤狀之基板面內之各個縱向及橫向中，以既定之間隔(例如0.01mm~1mm之間隔)來照射激發能量。可從所得之數據來獲得映射數據。亦可基於基板面內之映射數據，來挑選半導體元件之形成部位。Excitation energy can also be applied to multiple locations on the main surface of the aforementioned Group III nitride substrate. By applying excitation energy to multiple locations and mapping the half-value width of the band-edge emission within the substrate surface, it is possible to predict areas that do not meet a predetermined value and will result in low-quality semiconductor devices (e.g., defective areas with high leakage current). For example, excitation energy can be applied at predetermined intervals (e.g., 0.01 mm to 1 mm) in each of the longitudinal and lateral directions within the disk-shaped substrate surface shown in Figure 2. Mapping data can be generated from the resulting data. The mapping data within the substrate surface can also be used to select locations for semiconductor device formation.
C.製造方法C. Manufacturing Method
本發明一實施形態相關之III族元素氮化物基板之製造方法包含：準備具有基底基板與晶種膜之晶種基板之步驟；以及於晶種基板之晶種膜上生長摻雜有III族元素以外之元素之III族元素氮化物結晶之步驟。A method for manufacturing a Group III nitride substrate according to one embodiment of the present invention includes: preparing a seed crystal substrate having a base substrate and a seed crystal film; and growing a Group III nitride crystal doped with an element other than a Group III element on the seed crystal film of the seed crystal substrate.
圖3A至圖3C為表示一實施形態相關之III族元素氮化物基板之製造步驟之圖。圖3A為表示在具有彼此呈對向之上表面21a及下表面21b之基底基板21之上表面21a成膜出晶種膜22，並完成晶種基板20後之狀態。Figures 3A to 3C illustrate the manufacturing steps of a Group III nitride substrate according to one embodiment. Figure 3A shows the state after a seed film 22 is formed on the upper surface 21a of a base substrate 21 having opposing upper and lower surfaces 21a and 21b, completing the seed substrate 20.
作為上述基底基板，可使用例如具有可製造所欲之形狀、尺寸之III族元素氮化物基板之形狀、尺寸之基板。代表性而言，基底基板係成為直徑50mm~200mm之圓盤狀。基底基板之厚度為例如200μm~800μm。The base substrate can be a Group III nitride substrate with a desired shape and size, such as a substrate capable of producing the desired shape and size. Typically, the base substrate is in the shape of a disk with a diameter of 50 mm to 200 mm. The base substrate has a thickness of, for example, 200 μm to 800 μm.
作為基底基板，可使用任意適當之基板。基底基板較佳為以具有六方晶之結晶構造之單晶體所構成。例如，作為基底基板，較佳為使用以單晶氧化鋁所構成之藍寶石基板。Any suitable substrate can be used as the base substrate. The base substrate is preferably formed of a single crystal having a hexagonal crystal structure. For example, a sapphire substrate formed of single-crystal aluminum oxide is preferably used as the base substrate.
藍寶石基板之偏離角可設定為任意適當之角度。藍寶石基板之偏離角較佳為0.58°以下，更佳為0.48°以下，特佳為0.42°以下。藉由使用具有如此般之偏離角之藍寶石基板，便可獲得例如良率良好地(例如以高良率)製造品質優異之半導體元件之III族元素氮化物基板。另一方面，藍寶石基板之偏離角較佳為0.20°以上。藉由使用具有如此般之偏離角之藍寶石基板，便可良好地生長例如III族元素氮化物結晶。此處，藍寶石基板之偏離角意指藍寶石基板之主面相對於基準結晶面(c面)之傾斜角。The off-angle of the sapphire substrate can be set to any appropriate angle. The off-angle of the sapphire substrate is preferably 0.58° or less, more preferably 0.48° or less, and particularly preferably 0.42° or less. Using a sapphire substrate with such an off-angle makes it possible to obtain a Group III nitride substrate capable of manufacturing high-quality semiconductor devices with good yield (e.g., high yield). On the other hand, the off-angle of the sapphire substrate is preferably 0.20° or greater. Using a sapphire substrate with such an off-angle makes it possible to grow Group III nitride crystals well. Here, the off-angle of the sapphire substrate refers to the tilt angle of the main surface of the sapphire substrate relative to the reference crystal plane (c-plane).
上述晶種膜之厚度為例如0.2μm以上。就防止成膜時之回熔或消失之方面而言，晶種膜之厚度較佳為1μm以上，更佳為2μm以上。另一方面，晶種膜之厚度，就生產性之方面而言，較佳為10μm以下，更佳為5μm以下。The seed film has a thickness of, for example, 0.2 μm or greater. To prevent meltback or loss during film formation, the seed film thickness is preferably 1 μm or greater, more preferably 2 μm or greater. Furthermore, to improve productivity, the seed film thickness is preferably 10 μm or less, more preferably 5 μm or less.
作為構成晶種膜之材料，可採用任意適當之材料。作為構成晶種膜之材料，代表性而言，係使用III族元素氮化物。III族元素氮化物之細節如上所述。一實施形態中，係使用氮化鎵。較佳為使用藉由螢光顯微鏡觀察而被認為有黃色發光效果之氮化鎵。如此般之氮化鎵中，除了從能帶朝能帶之激發子遷移(UV)之外，還在2.2eV~2.5eV之範圍確認到峰值(黃色發光(YL)或黃色帶(YB))。Any suitable material can be used as the material constituting the seed film. Group III nitrides are typically used as the material constituting the seed film. Details of Group III nitrides are described above. In one embodiment, gallium nitride is used. Preferably, gallium nitride is used, as it is known to exhibit yellow luminescence when observed under a fluorescence microscope. Such gallium nitride exhibits not only band-to-band exciton migration (UV) but also a peak in the 2.2 eV to 2.5 eV range (yellow luminescence (YL) or yellow band (YB)).
晶種膜可藉由任意適當之方法來成膜。作為晶種膜之成膜方法，代表性而言，係使用氣相沉積法。作為氣相沉積法之具體例，可列舉：有機金屬化學氣相沉積(MOCVD：Metal Organic Chemical Vapor Deposition)法、氫化物氣相磊晶(HVPE)法、脈衝激發沉積(PXD)法、分子束磊晶(MBE)法、蒸鍍法、昇華法。該等當中，較佳為使用MOCVD。The seed film can be formed by any appropriate method. Typically, vapor deposition is used as the seed film formation method. Specific examples of vapor deposition methods include metal organic chemical vapor deposition (MOCVD), hydrogenated vapor phase epitaxy (HVPE), pulsed excitation deposition (PXD), molecular beam epitaxy (MBE), evaporation, and sublimation. Among these, MOCVD is preferred.
利用上述MOCVD所進行之晶種膜之成膜係依序包含例如第一形成步驟及第二形成步驟。具體而言，第一形成步驟中，係在溫度T1(例如450℃~550℃)下於基底基板上成膜未圖示之第一層(低溫成長緩衝層)，第二形成步驟中，係在較溫度T1要高之溫度T2(例如1000℃~1200℃)下成膜未圖示之第二層。第一層之厚度為例如20nm~50nm。第二層之厚度為例如1μm~5μm。The formation of the seed film using the aforementioned MOCVD process sequentially includes, for example, a first formation step and a second formation step. Specifically, in the first formation step, a first layer (not shown) (low-temperature growth buffer layer) is formed on a base substrate at a temperature T1 (e.g., 450°C to 550°C). In the second formation step, a second layer (not shown) is formed at a higher temperature T2 (e.g., 1000°C to 1200°C) than T1. The thickness of the first layer is, for example, 20nm to 50nm. The thickness of the second layer is, for example, 1μm to 5μm.
接著，於晶種基板20之晶種膜22上生長III族元素氮化物結晶而形成III族元素氮化物結晶層16，並如圖3B所示獲得疊層基板30。可對應於所欲之III族元素氮化物基板之厚度，來調整III族元素氮化物結晶之生長程度(III族元素氮化物結晶層16之厚度)。作為III族元素氮化物結晶之生長方向，可對應於用途、目的等，來選擇任意適當之方向。作為具體例，可列舉上述c面、a面、m面各自之法線方向、相對於上述c面、a面、m面而傾斜之面之法線方向。Next, a Group III nitride crystal is grown on the seed film 22 of the seed crystal substrate 20 to form a Group III nitride crystal layer 16, resulting in a laminated substrate 30 as shown in FIG3B . The growth extent of the Group III nitride crystal (the thickness of the Group III nitride crystal layer 16) can be adjusted according to the desired thickness of the Group III nitride substrate. The growth direction of the Group III nitride crystal can be selected in any appropriate direction according to the application and purpose. Specific examples include the normal direction of each of the aforementioned c-plane, a-plane, and m-plane, and the normal direction of a plane inclined relative to the aforementioned c-plane, a-plane, and m-plane.
III族元素氮化物結晶可藉由任意適當之方法來生長。作為III族元素氮化物結晶之生長方法，只要為可達成大致仿照上述晶種膜之結晶方位的結晶方位之方法的話，則無特別限定。作為III族元素氮化物結晶之生長方法之具體例，可列舉：有機金屬化學氣相沉積(MOCVD：Metal Organic Chemical Vapor Deposition)法、氫化物氣相磊晶(HVPE)法、脈衝激發沉積(PXD)法、分子束磊晶(MBE)法、昇華法等的氣相沉積法；助熔劑法、氨熱法、水熱法、溶膠凝膠法等的液相成長法。該等方法可單獨、或是組合二種以上來使用。Group III nitride crystals can be grown by any appropriate method. The method for growing Group III nitride crystals is not particularly limited, as long as it can achieve a crystal orientation that roughly mirrors the crystal orientation of the seed film described above. Specific examples of Group III nitride crystal growth methods include vapor phase deposition methods such as metal organic chemical vapor deposition (MOCVD), hydrogenated vapor phase epitaxy (HVPE), pulsed excited deposition (PXD), molecular beam epitaxy (MBE), and sublimation; and liquid phase growth methods such as flux methods, ammonothermal methods, hydrothermal methods, and sol-gel methods. These methods can be used alone or in combination of two or more.
作為III族元素氮化物結晶之生長方法，較佳為採用助熔劑法(例如Na助熔劑法)。如此般之生長方法之細節係記載於例如日本專利第5451085號公報，亦可適當調整所記載之生長方法之各種條件來進行生長。具體而言，III族元素氮化物結晶之生長可使用結晶製造裝置，並調整各種條件來進行，該結晶製造裝置具備：可供給加壓氮氣之耐壓容器；可在該耐壓容器內旋轉之旋轉台；以及載置於該旋轉台之外容器。A preferred method for growing Group III nitride crystals is a flux method (e.g., the Na flux method). Details of such growth methods are described, for example, in Japanese Patent No. 5451085, and growth can be performed by appropriately adjusting the various conditions of the described growth method. Specifically, Group III nitride crystals can be grown using a crystallization apparatus, adjusting various conditions. The crystallization apparatus comprises: a pressure-resistant container for supplying pressurized nitrogen gas; a rotating table that rotates within the pressure-resistant container; and an external container mounted on the rotating table.
利用助熔劑法所進行之III族元素氮化物結晶之生長，代表性而言，係使用作為生長容器之坩堝來進行。具體而言，係於坩堝內之既定位置配置上述晶種基板，進而填充原料。配置有晶種基板之坩堝，代表性而言，係在蓋上蓋體之狀態下，於包含氮氣之氛圍下，置於既定之壓力、溫度下，而被供於生長處理。The growth of Group III nitride crystals using the flux method is typically performed using a crucible as a growth vessel. Specifically, the seed crystal substrate is placed at a predetermined position within the crucible, and then the raw materials are filled. The crucible with the seed crystal substrate is typically covered with a lid and placed in a nitrogen atmosphere at a predetermined pressure and temperature for the growth process.
上述原料係包含例如助熔劑、III族元素、及摻雜劑之融液組成物。助熔劑較佳為包含鹼金屬與鹼土金屬之至少一者，更佳為包含金屬鈉。代表性而言，係混合助熔劑與金屬原料物質來使用。作為金屬原料物質，可使用單體金屬、合金、金屬化合物等，就處理之方面而言，較佳為使用單體金屬。The raw materials mentioned above are molten compositions containing, for example, flux, Group III elements, and dopants. The flux preferably contains at least one of an alkali metal and an alkali earth metal, more preferably metallic sodium. Typically, the flux is mixed with the metal raw material. The metal raw material can be a single metal, an alloy, or a metal compound. For ease of handling, single metals are preferred.
作為上述坩堝(包含蓋體)，可以能用於助熔劑法之任意適當之材質所形成。作為坩堝之材質，可列舉例如：氧化鋁、氧化釔、YAG(釔鋁石榴石)。又，坩堝之材質可為單晶，亦可為多晶(陶瓷)。陶瓷亦可為以HIP處理等提高相對密度後之所謂具有透光性者。The crucible (including the lid) can be made of any suitable material suitable for the flux method. Examples of crucible materials include alumina, yttrium oxide, and YAG (yttrium aluminum garnet). Furthermore, the crucible material can be single crystal or polycrystalline (ceramic). Ceramics can also be made translucent by increasing their relative density through HIP treatment or other means.
生長如上述般，可在包含氮氣之氛圍下進行。生長氛圍除了氮氣之外，還可包含其他氣體。作為其他氣體，較佳為使用氬氣、氦氣、氖氣等的非活性氣體。As described above, growth can be performed in an atmosphere containing nitrogen. The growth atmosphere may contain other gases in addition to nitrogen. Inert gases such as argon, helium, and neon are preferably used as these other gases.
生長時之氛圍壓力可設定在任意適當之壓力。生長時之氛圍壓力，例如就防止助熔劑蒸發之方面而言，較佳為10大氣壓以上，更佳為30大氣壓以上。另一方面，生長時之氛圍壓力，例如就防止生長裝置成為大規模裝置之方面而言，較佳為2000大氣壓以下，更佳為500大氣壓以下。The atmospheric pressure during growth can be set to any appropriate pressure. To prevent flux evaporation, the atmospheric pressure is preferably 10 atmospheres or higher, more preferably 30 atmospheres or higher. On the other hand, to prevent the growth apparatus from becoming a large-scale device, the atmospheric pressure is preferably 2000 atmospheres or lower, more preferably 500 atmospheres or lower.
生長時之氛圍溫度可設定在任意適當之溫度。生長時之氛圍溫度較佳為700℃~1000℃，更佳為800℃~900℃。The ambient temperature during growth can be set to any appropriate temperature. The preferred ambient temperature during growth is 700°C to 1000°C, more preferably 800°C to 900°C.
生長較佳為一邊使坩堝旋轉一邊進行。例如，將蓋上蓋體之坩堝收納於上述外容器並載置於上述旋轉台之上，再藉由旋轉旋轉台來使坩堝旋轉。Growth is preferably performed while the crucible is rotated. For example, the crucible with the lid is placed in the outer container and placed on the rotating table, which is then rotated to rotate the crucible.
在III族元素氮化物結晶之生長後，如圖3C所示，從基底基板21來將III族元素氮化物結晶(III族元素氮化物結晶層16)分離，而獲得獨立基板32。代表性而言，係如圖式般，獨立基板32可包含III族元素氮化物結晶16及晶種膜22。III族元素氮化物結晶可藉由任意適當之方法來從基底基板分離。作為III族元素氮化物結晶之分離方法，可列舉例如：在III族元素氮化物結晶之生長後之降溫步驟中利用與基底基板之熱收縮差來從基底基板自動分離之方法、藉由化學蝕刻來分離之方法、利用雷射光照射所進行之雷射剝離法。在藉由雷射剝離法來將III族元素氮化物結晶分離之情況，代表性而言，係從疊層基板30之基底基板21之下表面21b側來照射雷射光。又，亦可藉由使用研削、線鋸等的裁切機之裁切，來獲得獨立基板。After the growth of the Group III nitride crystals, as shown in FIG3C , the Group III nitride crystals (Group III nitride crystal layer 16) are separated from the base substrate 21 to obtain an independent substrate 32. Typically, as shown in the figure, independent substrate 32 may include the Group III nitride crystals 16 and a seed film 22. The Group III nitride crystals can be separated from the base substrate by any suitable method. Examples of methods for separating the Group III nitride crystals include: a method that utilizes the thermal contraction difference between the Group III nitride crystals and the base substrate during the cooling step after the growth of the Group III nitride crystals; a method that uses chemical etching for separation; and a laser stripping method using laser light irradiation. When separating Group III nitride crystals using laser ablation, laser light is typically applied from the lower surface 21b of the base substrate 21 of the stacked substrate 30. Alternatively, individual substrates can be obtained by cutting using a cutting machine such as a grinder or wire saw.
獨立基板32雖可維持原樣成為上述III族元素氮化物基板，但代表性而言，係對獨立基板32進行任意適當之加工，而獲得上述III族元素氮化物基板。While the independent substrate 32 can remain as the aforementioned Group III nitride substrate, typically, the independent substrate 32 is subjected to any appropriate processing to obtain the aforementioned Group III nitride substrate.
作為對上述獨立基板所進行之加工之一例，可列舉周緣部之研削加工(例如使用鑽石砂輪之研削加工)。代表性而言，係以藉由研削，來成為上述所欲之形狀、尺寸(例如具有所欲之直徑之圓盤狀)之方式來進行加工。An example of processing performed on the independent substrate is grinding of the peripheral portion (e.g., using a diamond grinding wheel). Typically, this is done by grinding to achieve the desired shape and dimensions (e.g., a disk with a desired diameter).
作為對上述獨立基板所進行之加工之另一例，可列舉主面(上表面、下表面)之研削、研磨(例如拋光研磨、化學機械研磨(CMP))等的加工。代表性而言，係以藉由研削及研磨，來成為所欲之厚度之方式而進行薄板化及平坦化。一實施形態中，係可藉由主面之加工來去除晶種膜22，而成為僅III族元素氮化物結晶層16(僅單一結晶成長層)之狀態。Another example of processing performed on the independent substrate is grinding and polishing (e.g., polishing or chemical mechanical polishing (CMP)) of the main surfaces (top and bottom surfaces). Typically, thinning and flattening are achieved by grinding and polishing to a desired thickness. In one embodiment, the main surface processing can be used to remove the seed film 22, leaving only the Group III nitride crystal layer 16 (a single crystal growth layer).
又，例如作為對上述獨立基板所進行之加工，可列舉外周緣之倒角加工、加工變質層之去除、可能起因於加工變質層之殘留應力之去除。Furthermore, examples of processing performed on the independent substrate include chamfering of the outer periphery, removal of the process-degraded layer, and removal of residual stress that may be caused by the process-degraded layer.
D.用途D. Application
上述III族元素氮化物基板可適用於任意適當之半導體元件。圖4為以HEMT元件為例來表示本發明一實施形態相關之半導體元件之概略構成之概略性的剖面圖。HEMT元件40具備：疊層構造43；以及設置於疊層構造43上之源極電極44、汲極電極45及閘極電極46，該疊層構造43依序包含：III族元素氮化物基板10、通道層41、及障壁層42。該等電極可分別為具有數十nm~數百nm左右之厚度之金屬電極。The aforementioned Group III nitride substrate can be applied to any suitable semiconductor device. Figure 4 is a schematic cross-sectional view illustrating the schematic structure of a semiconductor device according to one embodiment of the present invention, using a HEMT device as an example. HEMT device 40 comprises a stacked structure 43, and a source electrode 44, a drain electrode 45, and a gate electrode 46 disposed on the stacked structure 43. The stacked structure 43 sequentially comprises a Group III nitride substrate 10, a channel layer 41, and a barrier layer 42. These electrodes can be metal electrodes having a thickness of approximately tens to hundreds of nanometers.
疊層構造43可使各層進行異型接合。例如，通道層41及障壁層42可於III族元素氮化物基板10上方藉由磊晶成長來形成。此外，還存在有將此疊層構造稱為磊晶基板之情況。通道層41之厚度為例如50nm~5μm。障壁層42之厚度為例如2nm~40nm。The stacked structure 43 enables heterogeneous bonding of the layers. For example, the channel layer 41 and barrier layer 42 can be formed by epitaxial growth on the Group III nitride substrate 10. This stacked structure is sometimes referred to as an epitaxial substrate. The channel layer 41 has a thickness of, for example, 50 nm to 5 μm. The barrier layer 42 has a thickness of, for example, 2 nm to 40 nm.
作為構成通道層41及障壁層42之材料，可分別採用III族元素氮化物結晶。作為構成III族元素氮化物之III族元素，可使用例如Ga(鎵)、Al(鋁)、In(銦)。該等可單獨、或是組合二種以上來使用。一實施形態中，作為III族元素氮化物基板10可以摻雜有Ga以外之元素之氮化鎵所構成。於此情況，通道層41較佳為以氮化鎵所構成。然後，障壁層42較佳為以選自氮化鋁鎵、氮化鋁銦及氮化鋁銦鎵之至少一種所構成。The channel layer 41 and barrier layer 42 can each be made of a Group III nitride crystal. Group III elements such as Ga (gallium), Al (aluminum), and In (indium) can be used as the materials for the Group III nitride. These elements can be used alone or in combination. In one embodiment, the Group III nitride substrate 10 can be made of gallium nitride doped with an element other than Ga. In this case, the channel layer 41 is preferably made of gallium nitride. The barrier layer 42 is preferably made of at least one selected from aluminum-gallium nitride, aluminum-indium nitride, and aluminum-indium-gallium nitride.
通道層41及障壁層42可分別藉由任意適當之方法來形成。一實施形態中，通道層41及障壁層42可分別藉由MOCVD來形成。在藉由MOCVD來形成通道層41及障壁層42之情況，可使用有機金屬(MO)原料氣體作為III族元素源。例如，在藉由MOCVD，來形成氮化鎵層作為通道層41，且形成氮化鋁鎵層作為障壁層42之情況，作為Ga源及Al源，可分別使用三甲基鎵(TMG)及三甲基鋁(TMA)。然後，作為氮源，可使用氨氣。又，作為載體氣體，可使用氫氣或氮氣之至少一者。The channel layer 41 and the barrier layer 42 can each be formed by any suitable method. In one embodiment, the channel layer 41 and the barrier layer 42 can each be formed by MOCVD. When forming the channel layer 41 and the barrier layer 42 by MOCVD, an organometallic (MO) source gas can be used as a source of the Group III element. For example, when forming a gallium nitride layer as the channel layer 41 and an aluminum gallium nitride layer as the barrier layer 42 by MOCVD, trimethylgallium (TMG) and trimethylaluminum (TMA) can be used as the Ga source and Al source, respectively.Ammonia can be used as a nitrogen source. Furthermore, at least one of hydrogen or nitrogen can be used as a carrier gas.
雖未圖示，但於III族元素氮化物基板10與通道層41之間亦可配置有緩衝層。例如，緩衝層可在通道層成膜時形成，並可包含構成通道層之材料。Although not shown, a buffer layer may be disposed between the III-nitride substrate 10 and the channel layer 41. For example, the buffer layer may be formed during the formation of the channel layer and may include the material constituting the channel layer.
藉由III族元素氮化物基板10之能帶邊緣發光之半值寬滿足既定值，例如HEMT元件40便可良好地抑制漏電流。上述既定值亦可為例如半高全寬為6.5nm以下，亦可為長波長側之半高半寬為4.2nm以下。By ensuring that the half-width at half maximum of the band-edge emission of the III-nitride substrate 10 meets a predetermined value, leakage current in, for example, the HEMT device 40 can be effectively suppressed. This predetermined value can also be, for example, a full-width at half maximum of 6.5 nm or less, or a half-width at half maximum on the long-wavelength side of 4.2 nm or less.
[實施例][Example]
以下，便藉由實施例來具體說明本發明，但本發明並不被該等實施例所限定。此外，電阻率係藉由下述測定方法所測定之值。The present invention is described in detail below using examples, but the present invention is not limited to these examples. The resistivity is a value measured using the following measurement method.
<電阻率><Resistivity>
藉由電荷量時間變化並以非接觸方法來測定基板面內之電阻率。具體而言，係將基板載置於由探針與台座所構成之電容器之台座，使探針接近於基板附近，並施加脈衝幅100ns之脈衝電壓，在室溫(25℃)下，測定基板之電荷量隨時間之變化1秒鐘，而算出電阻率。The non-contact method measures the in-plane resistivity of a substrate by analyzing the temporal variation of charge. Specifically, the substrate is placed on a capacitor consisting of a probe and a base. The probe is brought close to the substrate and a pulse voltage with a 100ns amplitude is applied. At room temperature (25°C), the temporal variation of the substrate charge over one second is measured to calculate the resistivity.
〔實驗例1〕[Experimental Example 1]
(晶種基板之製作)(Seed crystal substrate preparation)
準備好具有各種偏離角(0.20°、0.28°、0.36°、0.39°、0.42°、0.43°、0.44°、0.46°、0.48°、0.52°、0.56°、0.58°及0.60°)之直徑3英寸的c面藍寶石基板。於各藍寶石基板上藉由MOCVD來成膜厚度2μm之氮化鎵膜，以製作晶種基板。3-inch diameter c-plane sapphire substrates with various offset angles (0.20°, 0.28°, 0.36°, 0.39°, 0.42°, 0.43°, 0.44°, 0.46°, 0.48°, 0.52°, 0.56°, 0.58°, and 0.60°) were prepared. A 2μm-thick gallium nitride film was deposited on each sapphire substrate using MOCVD to create a seed crystal substrate.
(氮化鎵結晶之生長)(Growth of GaN crystals)
氮化鎵結晶之生長係藉由結晶製造裝置來進行，該結晶製造裝置係具備：可供給加壓氮氣之耐壓容器；可在該耐壓容器內旋轉之旋轉台；以及載置於該旋轉台之外容器。將所得之晶種基板在氮氣氛圍之套手工作箱內配置於氧化鋁坩堝內。接著，將40g之金屬鎵、80g之金屬鈉與作為摻雜元素之鐵0.1g在套手工作箱內分別融解而填充於坩堝內，並將晶種基板浸漬於助熔劑融液，再以氧化鋁板來加蓋。在此狀態下，將坩堝放入不鏽鋼製之內容器，進而放入至可收納該內容器之不鏽鋼製之外容器，並以附氮氣導入管線之蓋體來關閉外容器。在此狀態下，將外容器載置於預先真空烘烤過且設置在結晶製造裝置內之加熱部之旋轉台之上，並於結晶製造裝置之耐壓容器蓋上蓋體而密閉。Gallium nitride crystals are grown using a crystallization apparatus equipped with a pressure-resistant vessel for supplying pressurized nitrogen gas, a rotating turntable within the pressure-resistant vessel, and an external container mounted on the turntable. The resulting seed crystal substrate is placed in an alumina crucible within a manifold box under a nitrogen atmosphere. Next, 40g of metallic gallium, 80g of metallic sodium, and 0.1g of iron as a dopant element are melted separately in the manifold box and filled into the crucible. The seed crystal substrate is then immersed in the flux solution and covered with an alumina plate. In this state, the crucible is placed into a stainless steel inner container, which is then placed into a stainless steel outer container that can accommodate the inner container. The outer container is closed with a lid equipped with a nitrogen inlet line. In this state, the outer container is placed on a pre-vacuum-baked rotating table in the heating section of the crystal production apparatus. The lid is then placed on the pressure-resistant container of the crystal production apparatus to seal it.
接著，操作加熱部(上段加熱器、中段加熱器及下段加熱器)，並以使加熱空間之溫度成為850℃之方式來進行加熱，並且從氮氣瓶將氮氣導入至耐壓容器內到成為4MPa為止，且使外容器進行水平旋轉。將此狀態保持35小時，使氮化鎵結晶成長。Next, the heating elements (upper, middle, and lower heaters) were operated to heat the heating space to 850°C. Nitrogen was introduced from a nitrogen cylinder into the pressure vessel until the pressure reached 4 MPa, and the outer vessel was rotated horizontally. This state was maintained for 35 hours to allow the gallium nitride crystals to grow.
之後，於自然冷卻至室溫並減壓至大氣壓後，開啟氧化鋁坩堝之蓋體，成長後之氮化鎵結晶與藍寶石基板呈自然剝離之狀態。如此一來，便獲得直徑3英寸且厚度1mm之氮化鎵結晶。After cooling naturally to room temperature and reducing the pressure to atmospheric pressure, the lid of the alumina crucible was removed, and the grown gallium nitride crystals naturally separated from the sapphire substrate. This resulted in a gallium nitride crystal with a diameter of 3 inches and a thickness of 1 mm.
之後，將氮化鎵結晶之自藍寶石基板剝離之側的面及其相反側之面使用鑽石研磨粒進行研磨而平坦化，獲得直徑3英寸、厚度0.5mm，且電阻率1×107Ω‧cm以上之摻雜Fe之氮化鎵基板。The surface of the gallium nitride crystal peeled from the sapphire substrate and the opposite surface were then polished and flattened using diamond abrasives, resulting in an Fe-doped gallium nitride substrate with a diameter of 3 inches, a thickness of 0.5 mm, and a resistivity of at least 1×107 Ω·cm.
〔實驗例2〕[Experimental Example 2]
除了摻雜元素換為Mn來取代Fe(將坩堝內填充有錳0.1g)以外，都與實驗例1同樣地獲得直徑3英寸、厚度0.5mm且電阻率1×107Ω‧cm以上之摻雜Mn之氮化鎵基板。The same procedures as in Experimental Example 1 were followed, except that the doping element was replaced with Mn (0.1 g of manganese was filled in the crucible). A Mn-doped gallium nitride substrate with a diameter of 3 inches, a thickness of 0.5 mm, and a resistivity of 1×107 Ω·cm or greater was obtained.
<評價><Evaluation>
就實驗例1及實驗例2所獲得之氮化鎵基板進行下述評價。The following evaluations were performed on the gallium nitride substrates obtained in Experimental Examples 1 and 2.
1.能帶邊緣發光之半值寬(半高全寬及半高半寬)1. Half-value width of band-edge luminescence (half-height full-width and half-height half-width)
就將紫外光雷射照射至所得之氮化鎵基板而獲得之光致發光，利用分光器來進行光譜測定，並求得能帶邊緣發光之峰值之半值寬。The photoluminescence obtained by irradiating the resulting gallium nitride substrate with ultraviolet laser light was measured using a spectrometer to measure the spectrum and determine the half-value width of the peak of the band edge luminescence.
具體而言，如圖5所示，將所得之氮化鎵基板(測定基板)56固定於試料台55，並在此狀態下於基板56之主面從雷射裝置51照射波長325nm之He-Cd雷射。雷射之照射係透過截波器52、消光板53及焦點距離100mm且φ50mm之聚光透鏡54，以入射角45°來照射至基板56之主面。來自基板56之光致發光係透過焦點距離100mm且φ150mm之聚光透鏡57、58來入射至分光器59。此外，圖5中之箭頭係表示雷射光之方向。Specifically, as shown in Figure 5 , the obtained gallium nitride substrate (measurement substrate) 56 was fixed to a sample stage 55. In this state, a He-Cd laser with a wavelength of 325 nm was irradiated onto the main surface of substrate 56 from a laser device 51. The laser light was irradiated at an incident angle of 45° through a wave chopper 52, a matte plate 53, and a focusing lens 54 with a focal distance of 100 mm and a diameter of 50 mm. Photoluminescence from substrate 56 was incident on a beam splitter 59 through focusing lenses 57 and 58 with a focal distance of 100 mm and a diameter of 150 mm. The arrows in Figure 5 indicate the direction of the laser light.
分光器59係安裝有光檢出器(光電子增倍管)60。將利用光檢出器60檢出之微弱訊號與截波器52同步並利用鎖相放大器61來增幅，而獲得發射光譜。此外，固定基板56之試料台55之位置係以使鎖相放大器61之檢出強度成為最大之方式來進行調整。此時基板56上之照射光之直徑為φ0.3mm左右。又，圖5中之虛線係表示同步訊號。The spectrometer 59 is equipped with a photodetector (photomultiplier) 60. The weak signal detected by the photodetector 60 is synchronized with the chopper 52 and amplified by the phase-locked amplifier 61 to obtain the emission spectrum. Furthermore, the position of the sample stage 55, which holds the substrate 56, is adjusted to maximize the detection intensity of the phase-locked amplifier 61. At this time, the diameter of the irradiated light on the substrate 56 is approximately φ0.3 mm. The dashed line in Figure 5 represents the synchronization signal.
藉由移動試料台55，而在基板面內以1mm之間隔來測定能帶邊緣發光，進而算出峰值之半值寬，並取得能帶邊緣發光之半值寬之映射數據。By moving the sample stage 55, the band-edge luminescence is measured at 1mm intervals within the substrate surface, and the half-value width of the peak is calculated. Mapping data for the half-value width of the band-edge luminescence is obtained.
2.漏電流2. Leakage current
(磊晶基板之製作)(Epitaxial substrate production)
藉由MOCVD，來於所得之氮化鎵基板之主面藉由磊晶成長來成膜氮化鎵(GaN)層及氮化鋁鎵(AlGaN)層，而製作磊晶基板。具體而言，將所得之氮化鎵基板配置於MOCVD裝置爐內之基座。將MOCVD爐內成為氫氣與氮氣之混合流，並在爐內壓力0.3atm下升溫至1100℃。在到達至1100℃後，使用氨氣與Ga原料氣體來成膜1μm之GaN層，之後，進而添加Al原料氣體來成膜20nm之AlGaN層(Al與Ga之組成比0.2：0.8)，而形成磊晶基板。在成膜後，使基板溫度下降至室溫，並復壓至大氣壓後，從MOCVD爐取出磊晶基板。Using MOCVD, gallium nitride (GaN) and aluminum gallium nitride (AlGaN) layers are epitaxially grown on the main surface of the resulting gallium nitride substrate to produce an epitaxial substrate. Specifically, the resulting gallium nitride substrate is placed on a susceptor within the MOCVD furnace. The MOCVD furnace is filled with a mixed flow of hydrogen and nitrogen, and the temperature is raised to 1100°C at a furnace pressure of 0.3atm. After reaching 1100°C, ammonia and Ga raw material gases are used to form a 1μm GaN layer. Subsequently, Al raw material gas is added to form a 20nm AlGaN layer (with an Al to Ga composition ratio of 0.2:0.8), forming the epitaxial substrate. After film formation, the substrate temperature is lowered to room temperature and re-pressurized to atmospheric pressure before the epitaxial substrate is removed from the MOCVD furnace.
(電晶體元件之製作)(Manufacturing of transistor components)
接著，使用磊晶基板來製作電晶體元件。在電極朝磊晶基板形成前，於所得之磊晶基板成膜厚度10nm之氧化矽膜來作為鈍化膜。接著，藉由光微影法，並以蝕刻來去除源極電極、汲極電極及閘極電極之形成預定部位之氧化矽膜。Next, the epitaxial substrate is used to fabricate transistor devices. Before electrodes are formed on the epitaxial substrate, a 10nm-thick silicon oxide film is deposited on the resulting epitaxial substrate as a passivation film. Next, photolithography and etching are used to remove the silicon oxide film from the areas where the source, drain, and gate electrodes will be formed.
接著，使用光微影法與反應性離子蝕刻(RIE)法，來將成為所得之各電晶體元件之邊界的部位蝕刻去除AlGaN層及GaN層至深度400nm左右為止。Next, photolithography and reactive ion etching (RIE) are used to etch away the AlGaN and GaN layers to a depth of approximately 400nm, which will form the boundaries of each transistor element.
接著，於AlGaN層上塗布光阻劑，並藉由光微影法來在形成源極電極及汲極電極之區域形成開口，再藉由真空蒸鍍法來將Ti、Al、Ni及Au之金屬膜分別以25nm、75nm、15nm、100nm之膜厚依序成膜，而形成多層構造。之後，使基板浸漬於有機溶劑或剝離液，並藉由剝離來去除光阻劑膜而獲得源極電極及汲極電極。接著，就提升源極電極及汲極電極之歐姆特性之方面而言，係將基板供於氮氣氛圍中於850℃下進行30秒鐘之熱處理。Next, photoresist is applied over the AlGaN layer, and photolithography is used to create openings in the areas where the source and drain electrodes will form. Metal films of Ti, Al, Ni, and Au are then deposited by vacuum evaporation to thicknesses of 25nm, 75nm, 15nm, and 100nm, respectively, to form a multilayer structure. The substrate is then immersed in an organic solvent or stripping solution, and the photoresist film is removed by stripping to form the source and drain electrodes. To improve the ohmic properties of the source and drain electrodes, the substrate is heat-treated at 850°C for 30 seconds in a nitrogen atmosphere.
接著，與源極電極及汲極電極之形成同樣地使用光微影法與真空蒸鍍法來將Pt及Au之金屬膜分別以30nm、100nm之膜厚來依序成膜，而獲得可成為蕭特基性金屬圖案之閘極電極。Next, similar to the formation of the source and drain electrodes, Pt and Au metal films are deposited sequentially using photolithography and vacuum evaporation to thicknesses of 30nm and 100nm, respectively, to form a gate electrode that can serve as a Schottky metal pattern.
如此一來，便製作形成有閘極寬度為1mm、源極與閘極之間隔為2μm、閘極與汲極之間隔為8μm、閘極長度為1μm之電極之電晶體元件。In this way, a transistor device with a gate width of 1mm, a source-gate spacing of 2μm, a gate-drain spacing of 8μm, and a gate length of 1μm was produced.
在如上述般製作之電晶體元件當中，就磊晶基板內之隨意挑選之15個樣本，來測定漏電流。在施加10V來作為源極、汲極間電壓，並將閘極電壓設為-4V且呈關閉狀態時，便將流通於源極、汲極間之電流作為漏電流。Among the transistor devices fabricated as described above, leakage current was measured for 15 randomly selected samples within the epitaxial substrate. When a 10V voltage was applied between the source and drain, and the gate voltage was set to -4V in the off state, the current flowing between the source and drain was taken as the leakage current.
作為一例，將在實驗例1中使用了偏離角0.43°之藍寶石基板時的評價結果示於表1及圖6、7。具體而言，係將基板內之任意16個元件之漏電流、從上述映射數據算出之各元件之基板內之位置之能帶邊緣發光之峰值的半高全寬及長波長側的半高半寬彙整於表1。As an example, the evaluation results for Experimental Example 1, using a sapphire substrate with an offset angle of 0.43°, are shown in Table 1 and Figures 6 and 7. Specifically, Table 1 summarizes the leakage current of 16 random elements within the substrate, the full width at half maximum (FWHM) of the peak band-edge emission at each element's position within the substrate, and the half-width at half maximum (FWHM) on the long-wavelength side, calculated from the mapping data above.
又，將關閉時之漏電流為小(4.57×10-8A/mm2)之元件所對應之能帶邊緣(波長364nm)附近之發射光譜表示於圖6之(1)，將漏電流大之(6.85×10-2A/mm2)元件所對應之能帶邊緣附近之發射光譜表示於圖7之(2)。此外，發射光譜係以最大值來正規化。Furthermore, the emission spectrum near the band edge (wavelength 364nm) corresponding to a device with a small leakage current when off (4.57×10-8 A/mm2 ) is shown in (1) of Figure 6, and the emission spectrum near the band edge corresponding to a device with a large leakage current (6.85×10-2 A/mm2) is shown in (2 ) of Figure 7. Furthermore, the emission spectra are normalized around the maximum value.
[表1]
由表1看來，在將漏電流未達1×10-6A/mm2評為良品時，使用了偏離角0.43°之藍寶石基板時之良品的比例為75%。同樣地，算出在實驗例1中使用偏離角不同之藍寶石基板所製作之氮化鎵基板個別之良品率。將算出結果彙整於表2。Table 1 shows that, when a leakage current of less than 1×10⁻⁶ A/mm⁻² is considered good, the yield rate for the sapphire substrate with an offset angle of 0.43° is 75%. Similarly, the yield rates for individual gallium nitride substrates fabricated in Experimental Example 1 using sapphire substrates with different offset angles were calculated. The results are summarized in Table 2.
[表2]
作為一例，將在實驗例2中使用了偏離角0.43°之藍寶石基板時的評價結果示於表3。具體而言，係將基板內之任意16個元件之漏電流、從上述映射數據算出之各元件之基板內之位置之能帶邊緣發光的半高全寬及長波長側的半高半寬彙整於表3。As an example, Table 3 shows the evaluation results for Experimental Example 2, using a sapphire substrate with an offset angle of 0.43°. Specifically, Table 3 summarizes the leakage current of 16 random elements within the substrate, the full width at half maximum (FWHM) of band-edge emission at each element's position within the substrate, and the half width at half maximum (FWHM) on the long-wavelength side, calculated from the mapping data above.
[表3]
由表3看來，在將漏電流未達1×10-6A/mm2評為良品時，使用偏離角0.43°之藍寶石基板時之良品的比例為63%。同樣地，算出在實驗例2中使用偏離角不同之藍寶石基板所製作之氮化鎵基板個別的良品率。將算出結果彙整於表4。Table 3 shows that, when a leakage current of less than 1×10⁻⁶ A/mm⁻² is considered good, the yield rate for the sapphire substrate with an offset angle of 0.43° is 63%. Similarly, the yield rates for individual gallium nitride substrates fabricated in Experimental Example 2 using sapphire substrates with different offset angles were calculated. The results are summarized in Table 4.
[表4]
[產業利用性][Industrial Utilization]
本發明之實施形態之III族元素氮化物基板可作為例如各種半導體器件之基板來使用。The Group III nitride substrate of the embodiment of the present invention can be used as a substrate for various semiconductor devices, for example.
10:III族元素氮化物基板 11:第一主面 12:第二主面 13:側面10: Group III nitride substrate11: First main surface12: Second main surface13: Side surface
| Application Number | Priority Date | Filing Date | Title |
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| JP2022-135354 | 2022-08-26 | ||
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| TW202425164A TW202425164A (en) | 2024-06-16 |
| TWI894609Btrue TWI894609B (en) | 2025-08-21 |
| Publication number | Priority date | Publication date | Assignee | Title |
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| US20140203266A1 (en) | 2005-06-30 | 2014-07-24 | Semiconductor Energy Laboratory Co., Ltd. | Light emitting device and electronic device |
| Publication number | Priority date | Publication date | Assignee | Title |
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| US20140203266A1 (en) | 2005-06-30 | 2014-07-24 | Semiconductor Energy Laboratory Co., Ltd. | Light emitting device and electronic device |
| Publication | Publication Date | Title |
|---|---|---|
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